Oxidized mixture of bio-based material and asphalt, a bio-based asphaltic material, and methods of making the same

ABSTRACT

A method of forming an asphalt mixture can include mixing a bio-source material and a bitumen source to form a bitumen mixture. The bitumen mixture can be mixed with a catalyst to form the asphalt mixture. Particles can be added to the asphalt mixture to form a roofing-grade asphalt mixture. In an embodiment, the bitumen source material can have a softening point of at least approximately 93° C. and a penetration distance no greater than approximately 25 dmm. In another embodiment, the roofing-grade asphalt mixture can have a softening point of at least approximately 104° C., a penetration distance no greater than approximately 12 dmm, a viscosity of at least approximately 3000 cps at a temperature of 204° C., or any combination thereof. The asphalt mixture can be applied to a base material to form a roofing product. The asphalt mixture can be applied as a pavement product.

CROSS-REFERENCE TO RELATED APPLICATION(S)

This application is a divisional of and claims priority under 35 U.S.C.§ 120 to U.S. patent application Ser. No. 15/365,713, entitled “OXIDIZEDMIXTURE OF BIO-BASED MATERIAL AND ASPHALT, A BIO-BASED ASPHALTICMATERIAL, AND METHODS OF MAKING THE SAME,” by Husnu M. KALKANOGLU etal., filed Nov. 30, 2016, now U.S. Pat. No. 10,934,456, whichapplication is a divisional of and claims priority under 35 U.S.C. § 120to U.S. patent application Ser. No. 13/729,222, entitled “OXIDIZEDMIXTURE OF BIO-BASED MATERIAL AND ASPHALT, A BIO-BASED ASPHALTICMATERIAL, AND METHODS OF MAKING THE SAME,” by Husnu M. KALKANOGLU etal., filed Dec. 28, 2012, now U.S. Pat. No. 9,540,544, which claimspriority under 35 U.S.C. § 119(e) to U.S. Application No. 61/582,324,entitled “OXIDIZED MIXTURE OF BIO-BASED MATERIAL AND ASPHALT, ABIO-BASED ASPHALTIC MATERIAL, AND METHODS OF MAKING THE SAME,” by HusnuM. KALKANOGLU et al., filed Dec. 31, 2011, of which each application isassigned to the current assignee hereof and incorporated herein byreference in their entireties.

FIELD OF THE DISCLOSURE

The present disclosure relates to asphalt mixtures, roofing products andmethods of making the roofing products and asphalt mixtures.

RELATED ART

Asphalt mixtures can find applications in the paving or roofingindustries. Roofing products can be in different forms, such as shinglesor membranes. The roofing products can include a base material and abituminous material. The base material can include wood, a woodderivative (e.g., paper), fiberglass, organic fibers (e.g., polyester),or the like. Conventionally, the bituminous material can includeasphalt, a filler, and potentially a plasticizer. A variety of fillershas been used including limestone, talc, fly ash, coal fines, or otherrelatively inert materials. Limestone has been most commonly used asfiller in roofing products due to its relatively low cost and itscompatibility with a wide variety of materials used for roofingproducts. Regardless of the composition of a roofing product, theroofing product must still be able to withstand the rigors of shippingand handling, installation, and exposure to outdoor environments formany years.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments are illustrated by way of example and are not limited in theaccompanying figures.

FIG. 1 includes a process flow diagram illustrating an exemplary methodof forming an asphalt mixture.

FIG. 2 includes an illustration of a cross-sectional view of a roofingproduct in accordance with an embodiment.

FIG. 3 includes an illustration of a cross-sectional view of a roofingproduct in accordance with another embodiment.

FIG. 4 includes an illustration of a cross-sectional view of a roofingproduct in accordance with a further embodiment.

FIGS. 5 a-5 f includes profiles of Gel Permeation Chromatography forvarious samples from embodiments.

Skilled artisans appreciate that elements in the figures are illustratedfor simplicity and clarity and have not necessarily been drawn to scale.For example, the dimensions of some of the elements in the figures maybe exaggerated relative to other elements to help to improveunderstanding of embodiments of the invention.

DETAILED DESCRIPTION

The following description in combination with the figures is provided toassist in understanding the teachings disclosed herein. The followingdiscussion will focus on specific implementations and embodiments of theteachings. This focus is provided to assist in describing the teachingsand should not be interpreted as a limitation on the scope orapplicability of the teachings.

The term “perimeter volume” is intended to mean a volume generallydefined by outer surfaces of an object. For example, a fiberglass matcan include glass fibers in the form of an open structure. The outersurfaces of the fiberglass mat are used to determine the perimetervolume. The volume occupied by only the glass fibers within thefiberglass mat may be substantially less than the perimeter volume.

The term “principal surfaces,” with respect to a roofing article orproduct, is intended to mean a pair of opposite surfaces of such roofingarticle or product, wherein one of the surfaces lies or would liefarther from a structure to which the roofing article or product isinstalled or intended to be installed, and the other surface of suchroofing article or article lies or would lie closer to a structure towhich the roofing article or article is installed or intended to beinstalled. When installed, the principal surface farther from thestructure may be directly exposed to an outdoor environment, and theother principal surface may contact the structure or a different roofingproduct that lies between the other principal surface and the structure.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a method,article, or apparatus that comprises a list of features is notnecessarily limited only to those features but may include otherfeatures not expressly listed or inherent to such method, article, orapparatus. Further, unless expressly stated to the contrary, “or” refersto an inclusive-or and not to an exclusive-or. For example, a conditionA or B is satisfied by any one of the following: A is true (or present)and B is false (or not present), A is false (or not present) and B istrue (or present), and both A and B are true (or present).

Also, the use of “a” or “an” is employed to describe elements andcomponents described herein. This is done merely for convenience and togive a general sense of the scope of the invention. This descriptionshould be read to include one or at least one and the singular alsoincludes the plural, or vice versa, unless it is clear that it is meantotherwise. For example, when a single item is described herein, morethan one item may be used in place of a single item. Similarly, wheremore than one item is described herein, a single item may be substitutedfor that more than one item.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. The materials, methods, andexamples are illustrative only and not intended to be limiting. To theextent not described herein, many details regarding specific materialsand processing acts are conventional and may be found in textbooks andother sources within the roofing product arts and correspondingmanufacturing arts.

An asphalt mixture or roofing product can include a bitumen mixture. Thebitumen mixture can include a bio-source material. The bitumen mixtureor roofing product can further include a bitumen source materialdifferent from the bitumen mixture. The asphalt mixture or roofingproduct can further include particles. In embodiments as describedherein, the bitumen mixture in the roofing-grade asphalt mixture mayallow use of the bitumen source material that may otherwise not be usedin making roofing-grade asphalt. In a particular embodiment, the bitumensource material has a softening point of at least approximately 95° C.and a penetration distance (100 g at 25° C., ASTM D5) no greater thanapproximately 25 dmm. The bitumen source material may be apetroleum-based asphalt, coal tar, or the like. The bio-source materialcan be a plant or animal derived product having an oil or fat content.In embodiments, the bio-source material can be plant or animal derivedlipid containing products such as vegetable oil, cooking oil, animalfat, whether new or used (recycled), or any combination thereof. In aparticular embodiment, the bio-source material includes a partiallyoxidized recycled vegetable oil. In another embodiment, the bio-sourcematerial can include fatty acids from animal or vegetable sources thatare esterified with sugars. For example, a highly esterified sucrosepolyester made from sugar and vegetable oils, e.g., soybean oil can beincluded as the bio-source material. In one embodiment, such materialcan be Sefose®. These products can be esters prepared from renewablefeedstocks by esterifying sucrose with fatty acid methyl esters (FAME).Examples of such products are described in U.S. Pat. No. 6,121,440,which is incorporated herein by reference in its entirety.

In one embodiment, oxidation or partial oxidation of a bio-sourcematerial includes oxidation of unsaturated hydrocarbons with molecularoxygen or other oxidants, followed by crosslinking reactions to formhigh molecular weight compounds.

The asphalt mixture may include particles, such as limestone, dolomite,talc, clay, coal fines, fly ash, gypsum, calcite, or any combinationthereof. The particles may be added before or after the oxidation isperformed. The oxidation of the bio-source material can be performed inthe presence of a catalyst. In a particular embodiment, the catalyst foroxidation is provided in a liquid form. In another embodiment, thecatalyst for oxidation is provided in solid form. An exemplary catalystincludes a metal salt. The metal of the metal salt can include cobalt,manganese, zirconium, vanadium, iron, calcium, nickel, copper, osmium,rhodium, rhenium, hafnium, or any combination thereof. Other suitablecatalysts include metal driers such as metal carboxylates wherein themetal is selected from the group of cobalt, manganese, calcium,zirconium, cerium, zinc, vanadium, iron, aluminum, strontium, barium,nickel, osmium, rhodium, rhenium, hafnium, lithium, or any combinationthereof. Non-limiting examples of such driers include cobalt octoate,cobalt linolate, vanadium naphthenate, vanadium octoate, zirconiumoctoate, cobalt naphthenate, lithium neodecanoate, cobalt octoate inmethyl soyate, manganese linoleate, and combinations thereof.

The asphalt mixture can be applied to a base material during formationof a roofing product, such as a roofing shingle, a roofing membrane,another suitable roofing product that includes an asphalt mixture, orthe like. If needed or desired, roofing granules, a parting agent, anadhesive, a release sheet, or any combination thereof may be applied toa surface of the combination of base material and roofing-grade asphalt.

The asphalt mixture can also be applied as a pavement or road surfacematerial during road construction or road maintenance. If needed ordesired, fillers, plasticizer, and other construction material, such assand, gravel, rubber particles, or any combination thereof may be added.

The combination of the bitumen mixture, the bitumen source materialdifferent from the bitumen mixture, and the particles can form aroofing-grade asphalt mixture, which is also referred to as a filledcoating. The roofing-grade asphalt mixture or filled coating can have asoftening point of at least approximately 104° C. (220° F.), apenetration distance no greater than approximately 12 dmm, a viscosityof at least approximately 3000 cps at a temperature of 177° C. (350°F.), or any combination thereof. The roofing-grade asphalt mixture canbe used to form a roofing product, such as a roofing shingle, a roofingmembrane, or another suitable roofing product that includes aroofing-grade asphalt.

In embodiments as described herein, the use of bitumen mixture may allowan off-specification bitumen source material to be used and still form aroofing-grade asphalt mixture of acceptable quality. Further, theasphalt mixture or roofing product can provide a more environmentallyacceptable solution to conventional roofing-grade asphalt that includesa petroleum-based asphalt as a sole bitumen source material. Theroofing-grade asphalt can use a renewable source that is less likely tobe irreversibly depleted. Similarly, fluctuations in the supply of suchbio-source materials may be less affected by political or other factors.Still further, the roofing-grade asphalt mixture can reduce the amountof spent bio-based materials that may otherwise need to be disposed ofby less environmentally acceptable means.

FIG. 1 includes a non-limiting, exemplary process flow that can be usedto form an asphalt mixture or a roofing product using a bitumen mixtureand a bitumen source material. In the embodiment of FIG. 1 , the methodincludes mixing a bitumen source and a bio-source material at block 102to form a bitumen mixture. The bitumen mixture can include at leastabout 5 wt % of the bio-source material, such as at least 11 wt %, or atleast about 15 wt % of the bitumen mixture. In another embodiment, thebitumen mixture can include an amount of the bio-source material nogreater than about 50 wt %, such as not greater than about 40 wt %, ornot greater than about 35 wt % of the bitumen mixture. In a particularembodiment, the bitumen source and bio-source material can be combinedand mixed using a mechanical mixer. The mixing may be performed as lowshear mixing or as high shear mixing. The low shear mixing can be in theform of blending, and the high shear mixing can be in the form ofmilling or dispersing. In another embodiment, mixing of the bitumensource and the bio-source material can be performed at a temperature ofat least approximately 175° C. (346° F.), at least approximately 180° C.(355° F.), or at least approximately 185° C. (364° F.). In anotherembodiment, mixing can be performed at a temperature of no greater thanapproximately 235° C. (455° F.), no greater than approximately 230° C.(446° F.), or no greater than approximately 225° C. (437° F.).

At block 122, the bitumen mixture can be partially oxidized by adding acatalyst. Oxidation of the bitumen mixture can achieve a desiredsoftening point, penetration distance, viscosity, or other suitablecharacteristics. In an embodiment, the oxidation can be performed suchthat a combination of the bitumen mixture and the catalyst has asoftening point of at least approximately 88° C. (190° F.), at leastapproximately 90° C. (194° F.), or at least approximately 93° C. (200°F.). In another embodiment, the oxidation can be performed such that acombination of the bitumen mixture and the liquid catalyst has asoftening point of not greater than approximately 110° C. (230° F.), notgreater than approximately 105° C. (221° F.), or not greater thanapproximately 102° C. (215° F.).

The oxidation of the bitumen mixture with the catalyst may be performedin the presence of a gas using air, nitrogen, oxygen, carbon dioxide,chlorine, another suitable oxidizing gas, or a combination of thesegases at a time and temperature such that any needed or desiredcharacteristic of the bio-source material or the bitumen source material(for example, softening point, penetration distance, viscosity, anothersuitable parameter, or any combination thereof) is achieved. In oneembodiment, the oxidation of the bitumen mixture with the catalyst canbe performed in the absence of air. In a particular embodiment, theoxidation may be performed at a temperature in a range of approximately100° C. (212° F.) to approximately 235° C. (455° F.). The oxidation ofthe bitumen mixture can be performed in the presence of a catalyst. In aparticular embodiment, the catalyst for oxidation is provided in aliquid form. In another particular embodiment, the oxidation can beperformed without the addition of a catalyst. The oxidation can beperformed until a needed or desired characteristic of the bitumenmixture, for example, softening point, penetration distance, viscosity,another suitable parameter, or any combination thereof is achieved.After reading this specification, skilled artisans will be able todetermine the particular conditions used for the oxidation. For thepurposes of this specification, an asphalt mixture material includes apartially oxidized bitumen source, such as a partially oxidizedpetroleum-based bitumen asphalt. Furthermore, the asphalt mixture canfurther include a partially oxidized vegetable oil, a partially oxidizedcooking oil, a partially oxidized animal oil, a partially oxidizedanimal fat, or any combination thereof. Moreover, the asphalt mixturecan include a partially oxidized bitumen source that is covalentlybonded to a partially oxidized bio-source material.

Referring to FIG. 1 , at least part of the bitumen source in block 102can include a bitumen source material that, by itself, may haveunacceptable characteristics for roofing-grade asphalt, which isreferred to as “off-spec asphalt.” The bitumen mixture may allow theoff-spec asphalt to be used in making an asphalt mixture having roadsurface grade or roofing grade that meets performance specifications andother desirable characteristics.

The bitumen source material can be different from the bitumen mixture.Such a bitumen source material can include a petroleum-based bitumen,coal tar, or another suitable bitumen source material. Unlike thebitumen mixture, the bitumen source material may be a non-renewablebitumen source material, as it may take many years (for example,hundreds of years, thousands of years, or longer) to form the bitumensource material. For a bitumen source material that has a softeningpoint that is too high and a penetration distance that is too low, sucha bitumen source material may not be oxidized. In a particularembodiment, the bitumen source material can include one or more than onebitumen source material, wherein at least one of the other bitumensource materials that may have unsuitable characteristics for aroofing-grade asphalt.

The off-spec bitumen source material may have a softening point that istoo high and a penetration distance that is too low. In an embodiment,the off-spec asphalt bitumen source material can have a softening pointof at least approximately 102° C. (215° F.) and a penetration distanceno greater than approximately 20 dmm. In a particular embodiment, thesoftening point can be at least 105° C. (221° F.) or at leastapproximately 108° C. (226° F.). In another particular embodiment, thepenetration distance may be no greater than approximately 17 dmm, nogreater than approximately 14 dmm, or no greater than approximately 11dmm. In yet another particular embodiment, the off-spec bitumen sourcematerial has a softening point no greater than approximately 110° C.(230° F.) and a penetration distance of at least approximately 10 dmm.

In a further embodiment, another bitumen source material may be used inaddition to or in place of the off-spec bitumen source material. Theother bitumen source material may meet the specifications forroofing-grade asphalt. The bitumen mixture can be used to extend theother bitumen source material.

Referring to block 122 of FIG. 1 , the bitumen mixture and the catalystmay be combined to obtain a desired softening point, penetrationdistance, viscosity, or another suitable characteristic as previouslydescribed. In a particular embodiment, the bitumen mixture and thecatalyst can be combined and mixed using a mechanical mixer. The mixingmay be performed as low shear mixing or as high shear mixing. The lowshear mixing can be in the form of blending, and the high shear mixingcan be in the form of milling or dispersing.

In an embodiment, adding of the catalyst can be performed at atemperature of at least approximately 175° C. (346° F.), at leastapproximately 180° C. (355° F.), or at least approximately 185° C. (364°F.). In another embodiment, mixing can be performed at a temperature ofno greater than approximately 235° C. (455° F.), no greater thanapproximately 230° C. (446° F.), or no greater than approximately 225°C. (437° F.). The combination of the bitumen mixture and the catalyst,without any filler material as described below, is hereinafter referredto as a raw coating material or asphalt mixture. Furthermore, theasphalt mixture including the bio-source material, the bitumen source,and the catalyst can be heated as shown in element 142 of FIG. 1 tofacilitate oxidation.

The roofing-grade asphalt mixture has a total bitumen contentcorresponding to the content of the bitumen mixture and the bitumensource material. In an embodiment, the bio-source material is at leastapproximately 5 wt %, at least approximately 11 wt %, or at leastapproximately 15 wt % of the total bitumen content. In anotherembodiment, the bitumen mixture is no greater than approximately 50 wt%, no greater than approximately 40 wt %, or no greater thanapproximately 35 wt % of the total bitumen content.

If needed or desired, an additive chemical can be used with the rawcoating material. The additive chemical can include a process oil, aplasticizer, a polymer modifier, a hardener, another suitable compound,or any combination thereof. The process oil can include a naphthenicoil, an aliphatic oil, or an aromatic oil, another suitable oil, or anycombination thereof. Another exemplary compound can include astyrene-butadiene-styrene, a styrene-ethylene-butylene-styrene, astyrene-isoprene-styrene, an acrylonitrile-butadiene-styrene, an atacticpolypropylene, an isotactic polypropylene, a high density polyethylene,an ethylene-polypropylene copolymer, another suitable plasticizer orpolymeric compound, or any combination thereof. A thermoplastic olefincan be formed using a metallocene catalyst and include a block copolymerpolypropylene, a polyethylene-propylene rubber, or another suitablematerial.

In an embodiment, the additive chemical may be added to the raw coatingmaterial. In another embodiment, the additive chemical can be added tothe bitumen mixture, the bitumen source, or the bitumen source materialbefore the raw coating material is formed. Typically, the additivechemical is in the form of a solid or a liquid at room temperature. Whenan additive chemical is used, the raw coating material may includesubstantially none of the additive chemical, at least approximately 5weight % of the additive chemical, or at least approximately 10 weight %of the additive chemical. In another embodiment, the raw coatingmaterial may include no greater than approximately 40 weight %, nogreater than approximately 30 weight %, or no greater than approximately25 weight % of the additive chemical.

In one embodiment, the oxidation can be performed such that the asphaltmixture can achieve a softening point no greater than approximately 120°C. (248° F.), no greater than approximately 115° C. (239° F.), or nogreater than 112° C. (234° F.). In yet another embodiment, the asphaltmixture can have a penetration distance of less than approximately 40dmm, less than approximately 30 dmm, or less than approximately 25 dmm.In another embodiment, the asphalt mixture can have a penetrationdistance of at least approximately 10 dmm, at least approximately 15dmm, or at least approximately 18 dmm. In a further embodiment, theoxidation can be performed such that the viscosity of the asphaltmixture, when measured at 177° C. (350° F.) is at least approximately500 cps, at least approximately 600 cps, or at least approximately 700cps. In another embodiment, the oxidation can be performed such that theviscosity of the asphalt mixture, when measured at 177° C. (350° F.) isat no greater than approximately 2000 cps, no greater than approximately1700 cps, or no greater than approximately 1500 cps. In addition, theoxidation can be performed such that the viscosity of the asphaltmixture, when measured at 204° C. (400° F.) is at least approximately100 cps, at least approximately 150 cps, or at least approximately 200cps. In another embodiment, the oxidation can be performed such that theviscosity of the asphalt mixture, when measured at 204° C. (400° F.) isat no greater than approximately 1000 cps, no greater than approximately700 cps, or no greater than approximately 500 cps.

A determination is made whether desired properties, such as softeningpoint, penetration distance, viscosity, or any other property (notillustrated) are obtained, at decision tree 144. The decision can bemade dependent from the determination of one or more of properties. Ifthe desired property or properties are obtained, the method continueswith the finishing operations. If the desired property or properties arenot obtained, such the process can be rerouted to previous steps. In anembodiment, an additional amount of bitumen mixture, bitumen sourcematerial, or catalyst can be added to the asphalt mixture and theasphalt mixture can undergo further heating as indicated in element 142of FIG. 1 . In another embodiment (not illustrated), a bitumen source,either the same or different from the bitumen source already added tothe asphalt mixture can be added. In yet another embodiment (notillustrated), after determining an undesired property, the mixture canundergo further heating without adding any other material.

Referring to block 162 of FIG. 1 , particles can be combined withasphalt mixture, and if present, the additive chemical, to form aroofing-grade asphalt mixture also referred to as a filled coating. Suchparticles can also be referred to as filler and can include limestone,dolomite, talc, clay, coal fines, fly ash, gypsum, calcite, anothersuitable filler material, or any combination thereof. In yet anotherembodiment, the particles may be added to the bio-source material, andif present, the additive chemical. In another embodiment, the particlescan be added to the bitumen mixture or the bitumen source material(after oxidation of the bitumen source material), before the raw coatingmaterial is formed. In a further embodiment, the particles can be addedto the asphalt mixture or also referred to as the raw coating material,before the additive chemical, if present, is combined with the rawcoating material. The combination of the raw coating material, theparticles, and if present, the additive chemical is referred to as thefilled coating material. In a particular embodiment, the roofing gradeasphalt mixture is the filled coating material, and can include anadditional material if needed or desired for a particular application.

In a shingle embodiment, the roofing-grade asphalt mixture can includeat least approximately 45 weight % of particles, at least approximately50 weight % of particles, or at least approximately 55 weight % ofparticles. In another shingle embodiment, the roofing-grade asphaltmixture may include no greater than approximately 80 weight % ofparticles, no greater than approximately 75 weight % of particles, or nogreater than approximately 70 weight % of particles. In a membraneembodiment, the roofing-grade asphalt mixture may include at leastapproximately 5 weight % of particles, or at least approximately 10weight % of particles. In another membrane embodiment, the roofing-gradeasphalt mixture may include no greater than approximately 70 weight % ofparticles, no greater than approximately 50 weight % of particles, or nogreater than approximately 40 weight % of particles.

The method can further include applying the mixture to a base structure,at block 182 of FIG. 1 . For roofing-grade asphalt mixture, the basematerial can include a fiberglass mat, a cellulose-based material, aceramic base material, a polymer fiber material, or the like. In aparticular embodiment, the cellulose-based material can include wood orpaper fibers. In another particular embodiment, the polymer fibermaterial can include a polyester. In another embodiment, the ceramicbase material can be vitreous or non-vitreous. In another embodiment,the ceramic base material can include ceramic fibers (e.g., glassfibers). In another embodiment, the ceramic base material can includematerial as described in U.S. Pat. No. 8,168,032, which is incorporatedherein by reference in its entirety. In a particular embodiment, thebase material includes an open structure. The open structure can allowthe roofing-grade asphalt mixture to flow within the open structure. Theopen structure can be in the form of pores, channels, interstitialopenings within a matrix, another suitable void, or any combinationthereof. Applying the roofing-grade asphalt mixture can be performedusing any one or more methods. In an embodiment, the base material canbe submerged into the roofing-grade asphalt mixture. In anotherembodiment (not illustrated), the open structure of the base materialcan be filled by spraying or coating the roofing-grade asphalt mixtureonto the base material.

When the base material includes an open structure, the open structuremay be partly or substantially completely filled with asphalt mixture.The outermost portions of the base material may or may not be exposedafter the asphalt mixture is applied. In an embodiment, the volume ofthe asphalt mixture is greater than a perimeter volume of the basematerial, and in another embodiment, the volume of the asphalt mixtureis no greater than the perimeter volume of the base material. In aparticular embodiment, a portion of a principal surface of the basematerial may be exposed; however, most of the structure or volume of thebase material may be embedded within or saturated with the asphaltmixture.

The method further includes finish processing of the asphalt product.Finishing can include one or more operations. For a roofing-gradeasphalt mixture or a filled coating, in an embodiment, roofing granulescan be applied to a surface of the coated base material. The roofinggranules can be used for ultraviolet radiation protection, coloration,impact resistance, fire resistance, another suitable purpose, or anycombination thereof. The roofing granules can include inert baseparticles that are durable, inert inorganic mineral particles, such asandesite, boehmite, coal slag, diabase, metabasalt, nephaline syenite,quartzite, rhyodacite, rhyolite, river gravel, mullite-containinggranules, sintered ceramic particles, another suitable inert material,or any combination thereof.

In another embodiment (not illustrated in FIG. 1 ), the roofing granulescan also include one or more surface coatings over the inert baseparticles. A surface coating can cover at least approximately 75% of thesurface of the inert base particle, and may cover at least approximately90% of the surface of the inert base particle. In a particularembodiment, the surface coating continuously covers the surface of theinert base particle, and such surface coating layer has a substantiallyuniform thickness. If more than one surface coating is used, asubsequent surface coating may cover an underlying surface coating tothe extent described with respect to the inert base particles.

If more than one surface coating is used, a surface coating closer tothe inert base particles can include a binder that can be inorganic ororganic. An inorganic binder can include a silicate binder, a titanatebinder, a zirconate binder, an aluminate binder, a phosphate binder, asilica binder, another suitable inorganic binder, or any combinationthereof. An organic binder can include a polymeric compound. In aparticular embodiment, an organic binder can include an acrylic latex,polyurethane, polyester, silicone, polyamide, or any combinationthereof. One or more additional organic binders of the same or differentcomposition can be used.

A surface coating can include a solar reflective material that helps toreflect at least some of the solar energy. For example, UV radiation canfurther polymerize or harden the asphalt within roofing product beingfabricated. A solar reflective material can include titanium dioxide,zinc oxide, or the like. Alternatively, the solar reflective materialcan include a polymeric material. In an embodiment, a polymer caninclude a benzene-modified polymer (e.g., copolymer including a styreneand an acrylate), a fluoropolymer, or any combination thereof. Othersolar reflective materials are described in U.S. Pat. No. 7,241,500 andU.S. Publication Nos. 2005/0072110 and 2008/0220167, all of which areincorporated by reference for their teachings of materials that are usedto reflect radiation (e.g., UV, infrared, etc.) from the sun.

A surface coating can include an algaecide or another biocide to helpreduce or delay the formation of algae or another organic growth. Thealgaecide or other biocide can include an organic or inorganic material.The algaecide or other biocide can include a triazine, a carbamate, anamide, an alcohol, a glycol, a thiazolin, a sulfate, a chloride, copper,a copper compound, zinc, a zinc compound, another suitable biocide, orany combination thereof. In a particular embodiment, the algaecide orother biocide can be included within a polymeric binder. The polymericbinder can include polyethylene, another polyolefin, an acid-containingpolyolefin, ethylene vinyl acetate, an ethylene-alkyl acrylatecopolymer, a polyvinylbutyral, polyamide, a fluoropolymer, an acrylic, amethacrylate, an acrylate, polyurethane, another suitable bindermaterial, or any combination thereof. Alternatively, the binder may be asolvent-based surface coating, a radiation curable surface coating, or atwo-part reactive surface coating. These alternative surface coatingsmay likewise include any of previously described polymeric materials.The same or different algaecide or other biocide can be used withindifferent surface coatings. An algaecide or another biocide is notrequired to be present in every surface coating of the roofing granules.In another particular embodiment, the algaecide or other biocide can bean inorganic material that is included within an inorganic binder, forexample, within an alkali metal silicate binder. An exemplary inorganicalgaecide or other biocide can include a metal (by itself), a metaloxide, a metal salt, or any combination thereof. The metallic elementused within the metal, metal oxide, or salt may include copper, zinc,silver, or the like. The metal salt can include a metal sulfate, a metalphosphate, or the like.

A surface coating can include a colorant or another material to providea desired optical effect. The colorant or other material can include ametal oxide compound, such as titanium dioxide (white), zinc ferrite(yellow), red iron oxides, chrome oxide (green), and ultramarine (blue),silver oxide (black), zinc oxide (dark green), or the like. In anotherembodiment, the colorant or other material may not be a metal-oxidecompound. For example, the colorant may include carbon black, zinc oraluminum flake, or a metal nitride.

An additional surface coating may be used for a different purpose notdescribed herein. For example, the surface coating can include adifferent oxide, nitride, oxynitride, carbide, oxycarbide, or anycombination thereof. After reading this specification, skilled artisanswill be able to determine if an additional function or purpose is to beserved by the roofing granules and whether an existing surface coatingor material within a surface coating serves such a function or purposeor if an additional surface coating or an additional material within anexisting surface coating would be needed or desired.

In addition to or in place of applying roofing granules, anotherfinishing operation can be performed. For example, after the roofinggranules are applied, another surface coating (not illustrated), similarto any single or combination of binders and surface coatings previouslydescribed with respect to the roofing granules, may be coated onto theroofing product after roofing granules have been applied. Such binder orsurface coating may have a solar reflective property, an algaecide orother biocide, a pigment or another appearance modifier, or anycombination thereof as previously described.

In another finishing operation, a parting agent can be applied to asurface of the roofing product. The parting agent helps to keep theroofing product from sticking to itself or sticking to othermanufacturing equipment, such as the equipment used in the web handlingor cutting operation. The parting agent can include particles of sand,talc, limestone, dolomite, slag, another relatively inert material, orany combination thereof. If the roofing product includes roofinggranules, the parting agent is applied to the surface of the roofingproduct opposite the roofing granules. After applying the roofinggranules, parting agent, or both are applied, the roofing product can beprocessed during a stamping or cutting operation to achieve a desiredshape for a finished roofing product. In particular, the finishedroofing product is in the form of a roofing shingle.

In another embodiment, a membrane-type roofing product can bemanufactured. The membrane-type roofing product has significantdifferences that are mostly seen with the finishing operations of themanufacturing process because the membrane-type roofing product istypically a self-adhesive product, although this is not a requirement.The finishing operations for a membrane-type roofing product can varydepending on the particular application.

In a particular embodiment, a principal surface of the membrane-typeroofing product can be directly exposed to an outdoor environment. Forthis particular application, roofing granules, a surface coating, orboth may be used. When the membrane-type roofing product is used as partof an underlayment or as a lower layer of a built-up roofing system,roofing granules may or may not be used. The membrane-type roofingproduct may be applied directly to a roof deck as a base sheet or anunderlayment. In this particular application, an adhesive can be used toprovide a good seal to help reduce the likelihood of water damage fromice dams. Accordingly, the finishing operation includes applyingadhesive and a release sheet to the roofing product. The adhesive caninclude a tackifier, such as polyvinylbutyral, a pressure sensitiveadhesive, another suitable compound, or any combination thereof. Apressure sensitive adhesive can include a silicone, a rubber, anacrylate, a bituminous adhesive, or the like. In a particularembodiment, a styrene-isoprene-styrene rubber composition can be used. Arelease sheet can be dispensed from a supply roll to the adhesive sideto form the roofing product.

In an alternative embodiment (not illustrated), an adhesive modifier canbe added to the roofing-grade asphalt that is first applied to the basestructure, or to an asphalt coating applied to the surface of theroofing product that will be closest to a roofing structure. Thus, aseparate adhesive application operation may be eliminated. In thisparticular embodiment, the release sheet would be applied to the surfacehaving the adhesive-modified roofing-grade asphalt.

In still another embodiment, no finishing operation may be performed,only one or some, but not all, of the previously-described finishingoperations may be performed, or another finishing operation may beperformed in addition to or in place of another finishing operation aspreviously described. Alternatively, a take-up roll may be used insteadof or before performing the stamping or cutting operation. After readingthis specification, skilled artisans will be able to configure amanufacturing line for the particular roofing product being formed.

After reading this specification, skilled artisans will appreciate thatmany other roofing products can be made using the concepts as describedherein. The particular materials, coatings, processes, and otherparameters can be tailored for the roofing products that are needed ordesired.

FIG. 2 includes an illustration of a cross-sectional view of thefinished roofing product 210. The finished roofing product 210 includesa coated base material 202 that includes any of the roofing-gradeasphalt mixtures as previously described. Roofing granules 222 areapplied to a principal surface of the coated base material 202, and aparting agent 224 is applied to an opposite principal surface of thecoated based material 202.

FIG. 3 includes an illustration of a cross-sectional view of thefinished roofing product 310. The finished roofing product 310 includesthe coated base material 202, roofing granules 222 and parting agent 224as previously described with respect to the roofing product 210. Unlikethe roofing product 210, the roofing product 310 includes aroofing-grade asphalt coating 302 that is disposed between the coatedbase material 202 and the roofing granules 222. The roofing-gradeasphalt coating 302 can include any of the roofing-grade asphaltmixtures as previously described. Thus, the roofing-grade asphaltcoating 302 may have substantially the same composition or a differentcomposition as compared to the roofing-grade asphalt mixture within thecoated base material 202.

In another embodiment, the roofing-grade asphalt coating 302 can includea conventional roofing-grade asphalt composition that is substantiallyfree of a bio-source material. In a further embodiment, the asphaltcompositions of the coated base material 202 and roofing-grade asphaltcoating 302 can be reversed. In particular, the coated base material 202can include a conventional roofing-grade asphalt composition, and theroofing-grade asphalt coating 302 can include the roofing-grade asphaltmixture that includes the bitumen mixture.

FIG. 4 includes an illustration of a cross-sectional view of thefinished roofing product 410. The finished roofing product 410 includesthe coated base material 202 as previously described with respect to theroofing product 210. Unlike the roofing product 210 that has the partingagent 224, the roofing product 410 includes a layer of adhesive 402 anda release sheet 404. The roofing product 410 can be a roofing membrane.When the roofing product 410 is an underlayment, roofing granules maynot be present. When the roofing product 410 has a principal surfacethat is exposed to outdoor conditions, roofing granules (not illustratedin FIG. 4 ) may be present along the principal surface opposite that ofthe layer of adhesive 402.

After reading this specification, skilled artisans will appreciate thatFIGS. 2 to 4 illustrate only a few potential roofing products that canbe formed with a roofing-grade asphalt mixture that includes a bitumenmixture. Other roofing products can be made without departing from theconcepts as described herein.

When properly prepared, the roofing-grade asphalt mixture can includebitumen mixture and still meet the stringent requirements in order toproduce roofing products that meet or exceed specifications. The bitumenmixture can be used to replace at least part of other bitumen sourcematerials, and in particular petroleum-based asphalt. Further, thebitumen mixture can be used to help recover an off-spec bitumen sourcematerial that may otherwise have been discarded. A wider variety ofbitumen source materials can be used. In addition, the cost offabricating roofing products may not fluctuate as much, and supplyconcerns may be less, as bitumen mixture may be produced domestically.

The embodiments as described herein can be used to produce a roofingproduct that can include a bio-source material that may be new or used.In an embodiment, the bio-source can be used oils, such as usedvegetable oil, used cooking oil, used animal oil, used animal fat, orother materials from other industries. For example, significant amountsof vegetable and animal oils are used or generated from restaurants.Such organic materials from biological sources may be limited value toothers, as such materials may not be suitable for use in producingfuel-grade products, paving grade asphalt, or the like. Roofing-grade orpavement-grade asphalt has different criteria, so materials that can berecycled or used for other industries may be used to form roofing-gradeasphalt. Thus, organic materials from biological sources, whether new orused, that may otherwise be of no significant commercial use in otherindustries may be used, recycled, processed, or the like for use inmaking bitumen mixture for a roofing-grade asphalt mixture.

Further, fabrication of roofing or pavement products is notsignificantly altered. The handling and application of the roofing-gradeasphalt mixture and further fabrication of the roofing product can besubstantially identical to that used for roofing products that includeconventional roofing-grade asphalt. Likewise, the handling andapplication of the pavement-grade asphalt mixture and furtherfabrication of the pavement product can be substantially identical tothat used for pavement products that include conventional pavement-gradeasphalt. Thus, significantly different equipment and processes may notneed to be used or integrated into an existing fabrication line.

Many different aspects and embodiments are possible. Some of thoseaspects and embodiments are described herein. After reading thisspecification, skilled artisans will appreciate that those aspects andembodiments are only illustrative and do not limit the scope of thepresent invention.

In a first aspect, a method of forming an asphalt mixture can includemixing a bitumen source and a bio-source material to form a bitumenmixture. In one embodiment, the method can further include adding acatalyst to the bitumen mixture to form an asphalt mixture. In anotherembodiment, the bio-source material can be present in an amount of atleast about 5 wt %, such as at least about 11 wt %, or at least about 15wt % of the bitumen mixture. In another embodiment, the bio-sourcematerial can be present in an amount of not greater than about 50 wt %,such as not greater than about 40 wt %, or not greater than about 35 wt% of the bitumen mixture.

In one embodiment, the method can further include agitating. Agitatingcan include stirring, propelling, shearing, impelling, bubbling themixture with a gas, or any combination thereof. In one embodiment, whenbubbling the mixture with a gas, the gas can include oxygen, air,nitrogen, carbon dioxide, chlorine, or any combination thereof. Inanother embodiment, the gas is free of air. In another embodiment, whenshearing the mixture, a gear pump or any mixer can be used.

In one further embodiment, the asphalt mixture formed by the method caninclude a roofing grade asphalt mixture. In one embodiment, the methodcan further include heating the asphalt mixture to at least about 100°C., such as at least about 120° C., at least about 140° C., or at leastabout 180° C. In another embodiment, the method can further includeheating the asphalt mixture to not greater than about 260° C., such asnot greater than about 240° C., not greater than about 220° C., notgreater than about 200° C., or not greater than about 180° C.

In one embodiment, the catalyst according to the method can include ametal salt. The metal can include cobalt, manganese, zirconium,vanadium, iron, calcium, nickel, copper, osmium, rhodium, rhenium,hafnium, or any combination thereof. In one other embodiment, the methodincludes a liquid catalyst that includes a metal salt, wherein the saltis a salt of an acid, the acid including naphthenic acid, octanoic acid,2-ethylhexanoic acid, ethylenediaminetetraacetic acid (EDTA), ethyleneglycol tetraacetic acid (EGTA), or any combination thereof. In anotherembodiment, the catalyst can be a liquid catalyst. In anotherembodiment, the liquid catalyst can include a solvent. The solvent caninclude ethanol, propanol, glycerol, toluene, xylene, mineral spirits,or any combination thereof.

In one further embodiment, the bio-source material can include an oil.The oil can include cooking oil, vegetable oil, animal fat, animal oil,or any combination thereof. In one particular embodiment, the oil caninclude recycled cooking oil, recycled vegetable oil, recycled animalfat, recycled animal oil, modified animal fat, modified vegetable oil,or any combination thereof.

Unsaturated fatty acid ester derived from natural sources such asvegetable oil/animal fat can be chemically modified to change or replaceparts of its structure. In a typical chemical modification, glycerolpart of fatty acid ester is replaced with any other alcohol (orcombination of alcohols) to make fatty acid ester. Such alcohols can bemonofunctional, difunctional, trifunctional, tetrafunctional, or ofhigher functionality such as sugar based moieties as previouslydescribed. Accordingly, modified oils include transesterified oils.Further, transesterified oils can still retain some hydroxylfunctionality. Unsaturated fatty acid ester can also be modified byblowing in presence of any oxygen containing gas or reacting with anyoxidation catalyst or exposing to UV light or heating at highertemperature or in any combination of these methods. Unsaturated fattyacid can also be further cross-linked by chemical reactions such as viaepoxidation, or via photocrosslinking etc.

In another embodiment, the method can further include adding an oxidizerto the bitumen mixture. The oxidizer can include oxygen, chlorine,hypochlorous acid (HOCl), a hypochlorite, a peroxide, a permanganate, orany combination thereof.

In one particular embodiment, the bitumen mixture formed according tothe method is substantially free of particulates. In another embodiment,the bitumen mixture formed according to the method has a single phase.

In one embodiment, the bitumen source comprises a petroleum-basedasphalt. In another embodiment, the bio-source material comprises apartially oxidized oil.

In another embodiment, the asphalt mixture also referred to as a rawcoating (unfilled coating) can have a softening point of at leastapproximately 88° C., a penetration distance no greater thanapproximately 30 dmm, a viscosity of not greater than approximately 2000cps at a temperature of 177° C., or any combination thereof. In onefurther embodiment, the asphalt mixture can have a softening point ofnot greater than approximately 102° C., a penetration distance nogreater than approximately 30 dmm, a viscosity of at least approximately500 cps at a temperature of 177° C., or any combination thereof. In yetone further embodiment, the softening point of the asphalt mixture canbe at least approximately 88° C., at least approximately 90° C., or atleast approximately 93° C. In another embodiment, the softening point ofthe asphalt mixture can be not greater than approximately 110° C., notgreater than approximately 105° C., or not greater than approximately102° C.

In another embodiment, the bitumen source material can have a softeningpoint of at least approximately 95° C. and a penetration distance nogreater than approximately 25 dmm. In one further embodiment, thesoftening point of the bitumen source material can be at leastapproximately 105° C. or at least approximately 108° C. In yet onefurther embodiment, the penetration distance of the bitumen sourcematerial can be no greater than approximately 30 dmm, no greater thanapproximately 28 dmm, or no greater than 25 dmm. In one embodiment, thesoftening point of the bitumen source material is no greater thanapproximately 110° C., and the penetration distance of the bitumensource material is at least approximately 10 dmm.

In one embodiment, the asphalt mixture has a total bitumen content,wherein the bio-source material can be at least approximately 5 wt %, atleast approximately 11 wt %, or at least approximately 15 wt % of thetotal bitumen content. In one further embodiment, the asphalt mixturehas a total bitumen content, wherein the bio-source material can be nogreater than approximately 50 wt %, no greater than approximately 40 wt%, or no greater than approximately 35 wt %.

In one embodiment, the mixing of the bitumen mixture with the catalystcan be performed at a temperature of at least approximately 175° C., atleast approximately 180° C., or at least approximately 185° C. In yetanother embodiment, the mixing of the bitumen mixture with the catalystcan be performed at a temperature no greater than approximately 235° C.,no greater than approximately 230° C., or no greater than approximately225° C.

In one embodiment, the asphalt mixture or raw coating can have aviscosity at 177° C. of at least approximately 500 cps, at leastapproximately 600 cps, at least approximately 700 cps, or at leastapproximately 800 cps. In another embodiment, the asphalt mixture or rawcoating can have a viscosity at 177° C. no greater than approximately2000 cps, no greater than approximately 1800 cps, no greater thanapproximately 1600 cps, or no greater than approximately 1500 cps.

In another embodiment, the method can further include adding particlesto the bitumen mixture or the asphalt mixture. The particles can includelimestone, dolomite, talc, clay, coal fines, gypsum, calcite, fly ash,or any combination thereof

In a second aspect, a method of forming a roofing product can includemixing a bio-source material with a bitumen source to form a bitumenmixture. The method can further include mixing the bitumen mixture witha catalyst and particles to form a roofing grade asphalt mixture. Themethod can further include applying the roofing-grade asphalt mixture toa base material.

In one embodiment, the bitumen source includes a petroleum-basedasphalt. In another embodiment, the roofing-grade asphalt mixture, whichincludes a filler, has a softening point of at least approximately 104°C., a penetration distance no greater than approximately 12 dmm, aviscosity of at least approximately 3000 cps at a temperature of 177°C., or any combination thereof. In another embodiment, the bitumensource material can have a softening point of at least approximately 95°C. and a penetration distance no greater than approximately 25 dmm. Inone embodiment, the softening point of the bitumen source material is atleast approximately 100° C. or at least approximately 108° C. Thepenetration distance of the bitumen source material can be no greaterthan approximately 25 dmm, no greater than approximately 22 dmm, or nogreater than 20 dmm. In another embodiment, the softening point of thebitumen source material can be no greater than approximately 110° C.,and the penetration distance of the bitumen source material is at leastapproximately 10 dmm.

In one embodiment, the bio source material can include a recycled oilmaterial. The recycled oil material can include a partially oxidizedoil. The oil can include cooking oil, vegetable oil, an animal oil,recycled cooking oil, recycled vegetable oil, recycled animal fat,modified vegetable oil, modified animal fat, or any combination thereof.

In another embodiment, the softening point of the roofing-grade asphaltmixture can be at least approximately 100° C., at least approximately103° C., or at least approximately 106° C. The softening point of theroofing grade asphalt mixture can be no greater than approximately 130°C., no greater than approximately 125° C., or no greater thanapproximately 120° C.

In another embodiment, the roofing-grade asphalt mixture or filledcoating has a total bitumen content, wherein the bio-source material canbe at least approximately 5 wt %, at least approximately 11 wt %, or atleast approximately 15 wt % of the total bitumen content. In anotherembodiment, the roofing-grade asphalt mixture has a total bitumencontent, wherein the bio-source material can be no greater thanapproximately 50 wt %, no greater than approximately 40 wt %, or nogreater than approximately 35 wt %.

In one embodiment, the mixing of the bitumen mixture with the catalystcan be performed at a temperature of at least approximately 175° C., atleast approximately 180° C., or at least approximately 185° C. Inanother embodiment, the mixing of the bitumen mixture with the catalystis performed at a temperature of no greater than approximately 235° C.,no greater than approximately 230° C., or no greater than approximately225° C.

In one embodiment, the roofing-grade asphalt mixture or filled coatingcan have a viscosity, measured at 204° C., of at least approximately3000 cps, at least approximately 3500 cps, at least approximately 3700cps, or at least approximately 3900 cps. In one embodiment, theroofing-grade asphalt mixture can have a viscosity, measured at 177° C.,of no greater than approximately 5000 cps, no greater than approximately4500 cps, no greater than approximately 4400 cps, or no greater thanapproximately 4300 cps.

In one embodiment, the base material can include a fiberglass mat, acellulose-based material, a ceramic base material, or a polymer fibermaterial. The cellulose-based material can include wood or paper fibers.The polymer can include a polyester.

In one embodiment, applying the roofing-grade asphalt mixture to thebase material can be performed such that the roofing-grade asphaltmixture substantially fills an open structure of the base material. Inan embodiment, applying the roofing-grade asphalt mixture to the basematerial can be performed such that at least 50% of the roofing-gradeasphalt material is outside of an open structure of the base material.

In one embodiment, the roofing product can include a roofing shingle.The particle content of the roofing shingle can be less than 80 weight %of the roofing-grade asphalt mixture. The particle can be added to theroofing product an amount of approximately 64 weight % to approximately70 weight % of the roofing-grade asphalt mixture.

In another embodiment, the roofing product can include a membrane-typeroofing product, and the particles are present at a content of less thanabout 60 weight % of the roofing-grade asphalt mixture. The content canbe less than about 50 wt %, less than about 40 wt %, less than about 30wt %, less than about 20 wt %, or less than about 10 wt %.

In one embodiment, the method can further include adding a plasticizer.The plasticizer can be added to the bitumen mixture. In anotherembodiment, the plasticizer can be added to the roofing grade asphaltmixture. In another embodiment, the plasticizer can be added to thebitumen mixture.

In one embodiment, the method further includes applying roofing granulesto an exposed surface of the roofing product after applying theroofing-grade asphalt mixture to the base material.

In one embodiment, the method further includes applying a release sheetto an exposed surface of the roofing product after applying theroofing-grade asphalt mixture to the base material. The method can beperformed such that the roofing product is in a form of a roofingshingle. In yet another embodiment, the method can be performed suchthat the roofing product is in a form of a roofing membrane.

In a third aspect, a roofing product includes a base material and aroofing-grade asphalt mixture. The roofing-grade asphalt mixture caninclude a bitumen mixture. The bitumen mixture can include a bio-sourcematerial and a catalyst residue. The bitumen mixture can further includea bitumen source material. The bitumen source material can be differentfrom the bitumen mixture. In one embodiment, the bitumen mixtureincludes a portion of the bio-source material being covalently bonded tothe bitumen source material.

In one embodiment, the roofing product can include a bitumen sourcematerial that has a softening point of at least approximately 90° C. anda penetration distance no greater than approximately 25 dmm. Thesoftening point of the bitumen source can be at least approximately 93°C. or at least approximately 95° C. In another embodiment, thepenetration distance of the bitumen source material is no greater thanapproximately 30 dmm, no greater than approximately 25 dmm, or nogreater than 20 dmm. The softening point of the bitumen source materialcan be no greater than approximately 110° C., and the penetrationdistance of the bitumen source material is at least approximately 10dmm. In one particular embodiment, the bitumen source comprises apetroleum-based asphalt.

In one embodiment, the roofing-grade asphalt mixture or filled coatingcan have a softening point of at least approximately 104° C., apenetration distance no greater than approximately 12 dmm, a viscosityof at least approximately 3000 cps at a temperature of 177° C., or anycombination thereof.

In another embodiment, the bio-source material can include a partiallyoxidized oil. The oil can include cooking oil, vegetable oil, an animaloil, recycled cooking oil, recycled vegetable oil, recycled animal fat,modified vegetable oil, modified animal fat, or any combination thereof.

In one embodiment, the softening point of the roofing-grade asphaltmixture or filled coating can be at least approximately 106° C., atleast approximately 110° C., or at least approximately 115° C. Thesoftening point of the roofing grade asphalt mixture can be no greaterthan approximately 130° C., no greater than approximately 125° C., or nogreater than approximately 120° C. In one embodiment, the roofing-gradeasphalt mixture has a total bitumen content, wherein the bio-sourcematerial is at least approximately 5 wt %, at least approximately 11 wt%, at least approximately 15 wt %, or at least approximately 20 wt % ofthe total bitumen content. In one embodiment, the roofing-grade asphaltmixture has a total bitumen content, wherein the bio-source material canhave a content of no greater than approximately 50 wt %, no greater thanapproximately 40 wt %, or no greater than approximately 35 wt %.

In one embodiment, the roofing product can include particles. Theparticles can include limestone, dolomite, talc, clay, coal fines,gypsum, calcite, fly ash, or any combination thereof. In one embodiment,the roofing product has a base material that includes a fiberglass mat,a cellulose-based material, a ceramic base material, or a polymer. Thecellulose-based material can include wood or paper fiber. In anotherembodiment, the polymer includes a polyester. In another embodiment, theceramic base material includes ceramic fibers. In one embodiment, theroofing-grade asphalt mixture substantially fills an open structure ofthe base material. In one embodiment, at least 50% of the roofing-gradeasphalt material is outside of an open structure of the base material.

In one embodiment, the roofing product can include a roofing shingle.The roofing shingle can include a particle content that is less than 80weight % of the roofing-grade asphalt mixture. In one particularembodiment, the particle content can include approximately 64 weight %to approximately 70 weight % of the roofing-grade asphalt mixture. Inanother embodiment, the roofing product includes a membrane-type roofingproduct, which has a particle content is less than 60 weight % of theroofing-grade asphalt mixture.

In one embodiment, the roofing-grade asphalt mixture further includes aplasticizer. Yet, in another embodiment, the roofing product furtherincludes roofing granules along a surface of the roofing product. Inanother embodiment, the roofing product can further include a releasesheet along a surface of the roofing product. In one embodiment, theroofing product can be in the form of a roofing shingle or in the formof a roofing membrane.

In one embodiment, the bio-source material can include unsaturated fattyacids, triglycerides, or a combination thereof. In another embodiment,the roofing grade asphalt can include a reaction product of thebio-source material and a catalyst.

In another embodiment, the catalyst residue can include a metal salt.The metal of the metal salt can include cobalt, manganese, zirconium,vanadium, iron, calcium, nickel, copper, zinc, osmium, rhodium, rhenium,hafnium, or any combination thereof. In one particular embodiment, thecatalyst residue includes a metal salt wherein the metal consistsessentially of a metal selected from cobalt, manganese, zirconium,vanadium, nickel, copper, zinc, osmium, rhodium, rhenium, hafnium, orany combination thereof. In another embodiment, the catalyst residueincludes two or more metal salts.

In a fourth aspect, a method of forming an asphalt mixture can includemixing a bitumen source material with a bio-source material to form abitumen mixture. The method can further include blowing the bitumenmixture with a gas to form a raw coating. In a modified version of thisaspect, a method of forming an asphalt mixture can include blowing abitumen source material with a gas and then mixing a bio-source materialto form a raw coating. In yet another modification, a method of formingan asphalt mixture can include blowing a bio-source material with a gasand then mixing a bitumen source material to form a raw coating. Also,one further modification comprises a method of forming an asphaltmixture that includes blowing a bitumen source material with a gas,separately blowing a bio-source material with a gas, and then mixing theblown bitumen source material and the blown bio-source material to forma raw coating. In yet another modification, after any of the abovementioned blowing and mixing sequences, further blowing may be performedto process the asphalt mixture to desired attributes. For example, themethod of forming an asphalt mixture can include blowing a bitumensource material with a gas, separately blowing a bio-source materialwith a gas, and then mixing the blown bitumen source material and theblown bio-source material to form a raw coating and continue to blow theraw coating with a gas.

In one embodiment, the method can further include adding particles. Theparticles can be added to the bitumen mixture. Alternatively, theparticles can be added to the raw coating. Moreover, particles can beadded to the bitumen mixture and the raw coating.

In another embodiment, the method can further include formulating theraw coating into a roofing grade asphalt mixture. In another embodiment,the method can include applying the roofing grade asphalt mixture to abase material. In yet one further embodiment, the method can includefinishing the roofing grade asphalt mixture applied to the base materialto form a roofing product.

In one embodiment, the gas can include air, oxygen, nitrogen, carbondioxide, chlorine, or any combination thereof. In another embodiment,the gas is free of air. In another embodiment, at least a portion of thebio-source material is covalently bonded to the bitumen source.

In another embodiment, the method can further include adding a catalystto the bitumen source material, the bio-source material, or the bitumenmixture.

EXAMPLES

Asphalt flux (Marathon Canton, Pen 150-200 dmm @ 25° C.) and recycledcooking oil (50/50 blend of soy and canola oils) were added to aone-liter Pyrex reaction vessel and thoroughly mixed together. Totalweight of each mixture was set at 800 gm. Three separate mixtures wereproduced, each with a different level of recycled cooking oil, at 10% or15% or 20% by weight. An air stream was introduced to the individualmixtures at 1 cfm via a metal tube with a perforated crossbar at the endto distribute bubbles throughout the mixture. Each individual mixturewas oxidized at 190° C. for 4 hrs. The properties of these oxidizedasphalt blends, in comparison to oxidized asphalt without any added oil,are listed in Table 1.

The results demonstrate that by oxidizing asphalt flux together with adifferent amount of recycled cooking oil, properties of the asphaltcoating can be custom designed to meet specific requirements. Forexample, the penetration values of oxidized asphalt mixture with 10%used cooking oil increased in comparison those of 100% asphalt, but thesoftening point and stain index were practically unchanged. However,when the recycled cooking oil amount was at 20 wt %, all threeproperties of the oxidized asphalt mixture had changed.

TABLE 1 Physical Properties of Oxidized Asphalts 90% 85% 80% 100%Asphalt/10% Asphalt/15% Asphalt/20% Property Asphalt Used oil Used oilUsed oil Soft Point, ° F. 208 207 206 205 Pen @ 32° F., dmm 4 8 11 12Pen @ 77° F., dmm 10 16 20 25 Pen @ 115° F., dmm 15 29 37 41 Stain Index4 4 5 6

Furthermore Gel Permeation Chromatography (GPC) was used to assesschanges in molecular weight profile of the samples after oxidationreactions. FIGS. 5 a and 5 b depict the profiles of recycled cooking oilbefore and after oxidation, respectively, depicting a large increase inthe molecular weight of the oxidized oil. FIGS. 5 c and 5 d are theprofiles of asphalt before and after oxidation, respectively. Hereagain, after oxidation the GPC profile depicts a large broad shoulder inthe shorter elution time region, corresponding to higher molecularweight, after oxidation.

FIG. 5 e is the GPC profile of the asphalt mixture containing 20% byweight of oxidized used cooking oil (as in FIG. 5 b ) and 80% by weightof oxidized asphalt coating (as in FIG. 5 d ). The mixture of FIG. 5 eis a physical mixture of oxidized asphalt and oxidized used cooking oilthat were oxidized separately prior to mixing. FIG. 5 f is the GPCprofile of the asphalt mixture by first pre-blending 20% by weight ofused cooking oil (as in FIG. 5 a ) and 80% by weight of asphalt flux (asin FIG. 5 c ), then oxidizing them together. The comparison of FIGS. 5 eand 5 f reveals that the latter compound has a different molecularweight profile that includes at least two additional peaks appearing onthe shoulder at around 11 min and 12 min elution times, indicating thathigh molecular weight components were polymerized within this asphaltmixture. By examining all these molecular weight profiles, it shows thatpre-blending two separate components, the oil and the asphalt, togetherfollowed by oxidation (as in FIG. 5 f ) results in a composition that isdifferent and distinct from one by simply mixing two components thathave already been oxidized separately.

Air Blowing Soybean Oil with Asphalt

In a control experiment, 800 g of Ergon flux, obtained from Ergon Inc.,Vicksburg, Ms, was placed in a 2 L container and air blown through anair flow spider without further agitation to a final softening point of201° F. The process includes (a) heating asphalt flux to 460-480° F. for5-7 hours (b) spray air at 1 cfm through hot asphalt for a period oftime until the desired softening point is achieved. Air blown asphalt,also known as raw coating, was then further mixed with limestone as amineral stabilizer to make a 69 vol % filled coating.

In a separate experiment, Ergon flux was mixed with 10 wt % soybean oil(unrefined, generic) and air blown to a softening point of 207° F.Limestone as a mineral stabilizer was mixed with the raw coating to makea 69 vol % filled coating. Table 2 summarizes the physical properties.

TABLE 2 Properties of Air blown asphalt with or without soybean oil RawRaw Coating Filled Filled Coating Ergon Coating with 10% coating fromsoybean Material Flux (control) soybean oil (control) oil treated fluxFiller % 69% 69% Soft Point/° F. 98 201 207 247 239 Pen. @77° F./ 250 1925 5 8 dmm Vis. @ 400° F./cps 295 383 4733 3775 Vis. @ 415° F./cps 35002875 Vis. @ 425° F./cps 188 258 Vis. @ 430° F./cps 2600 2233 Vis. @ 450°F./cps 143 158

As can be seen in Table 2. addition of soybean oil makes filled coatingsofter (lower viscosity, higher penetration distance, lower softeningpoint) and improve its flexibility. Viscosity was measured with aBrookfield rotational viscometer model DV-E using spindle S27, Speed 30rpm.

Air Blowing Sefose with Asphalt

Sefose® is highly esterified sucrose polyester made from sugar and fattyacid of vegetable oil. Sefose 1618U was obtained from P&G Chemicals,Cincinnati, Ohio Shell Flux, Shell, Mobile, Ala. was mixed with 10 wt %Sefose 1618U and air blown to softening point of 212° F. as describedabove in the Example for soybean oil. Table 3 summarizes the results.

TABLE 3 Properties of Air blown asphalt with or without Sefose ® RawCoat. Raw coating with Material Flux (Control) 10% Sefose Soft Point/°F. 96 211 212 Pen. @ 77° F./dmm. 262 17 18 Vis. @ 350° F./cps 1085 Vis.@ 375° F./cps 498 408 Vis. @ 400° F./cps 268 Vis. @ 415° F./cps Vis. @425° F./cps 150 Vis. @ 430° F./cps Vis. @ 450° F./cps 70

As can be seen in Table 3, addition of Sefose® renders a slightly softerraw coating.

Note that not all of the activities described above in the generaldescription or the examples are required, that a portion of a specificactivity may not be required, and that one or more further activitiesmay be performed in addition to those described. Still further, theorder in which activities are listed is not necessarily the order inwhich they are performed.

Benefits, other advantages, and solutions to problems have beendescribed above with regard to specific embodiments. However, thebenefits, advantages, solutions to problems, and any feature(s) that maycause any benefit, advantage, or solution to occur or become morepronounced are not to be construed as a critical, required, or essentialfeature of any or all the claims.

The specification and illustrations of the embodiments described hereinare intended to provide a general understanding of the structure of thevarious embodiments. The specification and illustrations are notintended to serve as an exhaustive and comprehensive description of allof the elements and features of apparatus and systems that use thestructures or methods described herein. Separate embodiments may also beprovided in combination in a single embodiment, and conversely, variousfeatures that are, for brevity, described in the context of a singleembodiment, may also be provided separately or in any subcombination.Further, reference to values stated in ranges includes each and everyvalue within that range. Many other embodiments may be apparent toskilled artisans only after reading this specification. Otherembodiments may be used and derived from the disclosure, such that astructural substitution, logical substitution, or another change may bemade without departing from the scope of the disclosure. Accordingly,the disclosure is to be regarded as illustrative rather thanrestrictive.

What is claimed is:
 1. A roofing product comprising: a base material;and a roofing-grade asphalt mixture comprises: a bitumen mixtureincluding a bio-source material and bitumen source material; a catalystresidue comprising a metal salt, the metal salt comprising the salt ofan acid, the acid comprising octanoic acid, 2-ethylhexanoic acid,ethylenediaminetetraacetic acid (EDTA), ethylene glycol tetracetic acid(EGTA), or any combination thereof; and a filler.
 2. The roofing productof claim 1, wherein the bitumen mixture comprises a portion of thebio-source material being covalently bonded to the bitumen sourcematerial.
 3. The roofing product of claim 1, wherein the bitumen sourcematerial has a softening point of at least approximately 90° C. and apenetration distance no greater than approximately 30 dmm.
 4. Theroofing product of claim 1, wherein the bitumen source material has asoftening point of not greater than approximately 110° C., and thepenetration distance of the bitumen source material is at leastapproximately 10 dmm.
 5. The roofing product of claim 1, wherein thebitumen source comprises a petroleum-based asphalt.
 6. The roofingproduct of claim 1, wherein the roofing-grade asphalt mixture has asoftening point of at least approximately 104° C., a penetrationdistance no greater than approximately 12 dmm, a viscosity of at leastapproximately 3000 cps at a temperature of 177° C., or any combinationthereof.
 7. The roofing product of claim 1, wherein the bio-sourcematerial comprises a partially oxidized oil, the oil including cookingoil, vegetable oil, animal oil, recycled cooking oil, recycled vegetableoil, recycled animal fat, modified vegetable oil, modified animal fat,or any combination thereof.
 8. The roofing product of claim 1, whereinthe roofing-grade asphalt mixture has a total bitumen content, whereinthe bio-source material is at least approximately 5 wt % of the totalbitumen content.
 9. The roofing product of claim 1, wherein theroofing-grade asphalt mixture has a total bitumen content, wherein thebio-source material has a content of no greater than approximately 50 wt% of the total bitumen content.
 10. The roofing product of claim 1,wherein at 204° C., the roofing-grade asphalt mixture has a viscosity ofat least approximately 3000 cps.
 11. The roofing product of claim 1,wherein at 204° C., the roofing-grade asphalt mixture has a viscosity nogreater than approximately 5000 cps.
 12. The roofing product of claim 1,wherein the filler comprise particles.
 13. The roofing product of claim12, wherein the particles comprise limestone, dolomite, talc, clay, coalfines, gypsum, calcite, fly ash, or any combination thereof.
 14. Theroofing product of claim 1, wherein the base material comprises afiberglass mat, a cellulose-based material, a ceramic base material, ora polymer.
 15. The roofing product of claim 1, wherein the roofing-gradeasphalt mixture substantially fills an open structure of the basematerial.
 16. The roofing product of claim 1, wherein at least 50% ofthe roofing-grade asphalt material is outside of an open structure ofthe base material.
 17. The roofing product of claim 1, wherein theroofing-grade asphalt mixture further comprises a plasticizer.
 18. Theroofing product of claim 1, wherein the bio-source material comprisesunsaturated fatty acids, triglycerides, or a combination thereof. 19.The roofing product of claim 1, wherein the roofing grade asphaltcomprises a reaction product of the bio-source material and a catalyst.20. The roofing product of claim 1, wherein the metal of the metal saltcomprises cobalt, manganese, zirconium, vanadium, iron, calcium, nickel,copper, zinc, osmium, rhodium, rhenium, hafnium, or any combinationthereof.